Catalytic combustion of toluene on platinum-containing monolithic carbon aerogels

Monolithic organic aerogels were prepared by the sol–gel procedure from the polymerisation reaction of resorcinol and formaldehyde in water. The organic aerogels were heat treated in inert atmosphere at either 500 or 1000 °C to obtain the carbon aerogels. The catalysts were prepared by impregnation with an aqueous solution of [Pt(NH₃)₄]Cl₂ or by dissolving this salt in the initial aerogel mixture. Supported catalysts were pretreated in He at 400 °C or H₂ at 300 °C before their characterization by H₂ chemisorption, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy or before testing their catalytic activity. Catalyst activities in toluene combustion were evaluated by conversion versus temperature (light-off curves) and conversion versus time catalytic tests. In the case of catalysts prepared by impregnation, the light-off curves for the total combustion of toluene were shifted to lower temperatures with increasing Pt particle size. This suggests that the reaction was sensitive to the Pt structure within the dispersion range of these catalysts. However, the reverse occurred with catalysts prepared by mixing the precursor in the initial aerogel mixture. Results found could be due to the different surface Pt content of these catalysts as revealed by X-ray photoelectron spectroscopy. This difference was related to the growth of large three-dimensional Pt particles on the surface of the less dispersed catalyst. This means that there is a critical Pt particle size above which the toluene combustion activity decreases with increasing Pt particle size, due to the reduction in active surface sites available for the combustion reaction. Other effect that might influence the activity of these last catalysts is the encapsulation of some Pt particles by the carbon matrix.     

Catalytic clean-up of emissions from small-scale combustion of biofuels

A knitted silica-fibre was prepared and used as support for combustion catalysts. Different Pd–MeO and Pt–MeO (Me=Ni, Co, Cu and Mn) catalysts were prepared, and their catalytic activities were investigated in the conversion of gas mixtures consisting of methane, ethene, naphthalene (model PAH), carbon monoxide, carbon dioxide, nitrogen and water vapour in the temperature range 150–800°C. Combinations of Pd–Ni and Pt–Ni were found to result in decreased light-off temperatures in methane combustion. The Pd–Ni/silica-fibre catalyst exhibited a light-off temperature in methane combustion of ca 220°C lower than that obtained over the Pd/silica-fibre catalyst. Deactivation of the catalysts was observed by subjecting the catalysts to reaction mixture flow at 800°C for 6 h. For the Pd-containing catalysts, the deactivation was considered to be due to both support and metal sintering as well as changes in the nature of the Pd–O species. The catalysts were characterised by N₂-adsorption, H₂-adsorption, O₂–TPD and H₂–TPR.     

Comparative study of Pt-based catalysts on different supports in the low-temperature de-NOx-SCR with propene

Pt-based catalysts have been prepared using supports of different nature (γ-Al₂O₃, ZSM-5, USY, and activated carbon (ROXN)) for the C₃H₆-SCR of NO_x in the presence of excess oxygen. Nitrogen adsorption at 77 K, pH measurements, temperature-programmed desorption of propene, and H₂ chemisorption were used for the characterization of the different supports and catalysts. The performance of these catalysts has been compared in terms of de-NO_x activity, hydrocarbon adsorption and combustion at low temperature, and selectivity to N₂. Maximum NO_x conversions for all the catalysts were achieved in the temperature range of 200–250°C. The order of activity was, Pt-USY>Pt/ROXNPt-ZSM-5Pt/Al₂O₃. At temperatures above 300°C only Pt/ROXN maintains a high activity caused by the consumption of the support, while the other catalysts present a strong deactivation. Propene combustion starts at the same temperature for all the catalytic systems (160°C). Complete hydrocarbon combustion is directly related to the acidity of the support, thus determining the temperature of the maximum NO_x reduction. The support play an important role in the reaction mechanism through the hydrocarbon activation. N₂O formation was observed for all the catalysts. N₂ selectivity ranges from 15 to 30% with the order, Pt/ROXN>Pt-USYPt/Al₂O₃>Pt-ZSM-5. The catalytic systems exhibit a stable operation under isothermal conditions during time-on-stream experiments.     

Catalytic combustion of methane over palladium exchanged zeolites

Palladium cation exchanged zeolites (ZSM-5, mordenite and ferrierite) were studied as catalysts for methane combustion. Pd-zeolites showed much higher activities than PdO/Al₂O₃. For comparable palladium loadings, PdO/Al₂O₃ requires a reaction temperature of ca. 70–80°C higher than Pd-ZSM-5 for conversions between 50–100%. The catalytic activity of Pd-ZSM-5 seems to be related to its reducibility. Temperature-programmed reduction experiments with carbon monoxide showed a lower reduction temperature (ca. 157°C) for Pd-ZSM-5 than for PdO/Al₂O₃ (225°C). Further, the positioning of the palladium by ion exchange offers a highly dispersed form of Pd^II supported on the high surface area zeolite.     

Low-temperature complete oxidation of BTX on Pt/activated carbon catalysts

The catalytic destruction of volatile organic compound (VOC) benefits from a low oxidation temperature due to less energy consumption. In this study, activated carbon-supported Pt catalysts were prepared for benzene, toluene and xylene (BTX) deep oxidation at below 200°C. Activated carbon can serve as a media for concentrating VOC. The carbon supports were heated to 400 or 800°C under N₂ flow and washed with HF acid to remove surface impurities and/or minerals. The 0.3 wt.% Pt/activated carbon catalysts were prepared by the incipient wetness method, followed by H₂ reduction at 300°C for 2 h. The catalytic oxidation was conducted with a BTX concentration ranging from 640 to 2000 ppmv in air at volume hour space velocity (VHSV) of approximately 21 000 h⁻¹. The light-off curves were very steep and the light-off temperatures ranged between 130 and 150°C, well below those of the Pt/Al₂O₃ catalyst. The oxidation activity was promoted because of a higher surface BTX concentration due to the adsorption capability of activated carbons. Moisture reduces the activity only slightly due to the hydrophobicity of activated carbon. Generally, the Pt catalysts with thermally-treated activated carbon had lower ignition temperatures. Experimental results indicated that high-temperature pretreatment of activated carbon could effectively increase the catalyst activity. Meanwhile, X-ray photoelectron spectroscopy (XPS)/secondary ion mass spectroscopy (SIMS) investigation revealed that the graphitized surface might play a role in catalytic activity. Finally, this work suggested a reaction mechanism based on the adsorption-migration of hydrocarbons to reveal the enhanced activity of activated carbon support.     

Kinetics of PdO combustion catalysis

The kinetics of the catalytic combustion of methane by supported palladium oxide catalysts (2 wt.-% Pd/La₂O₃·11A1₂O₃ and 5 wt.-%Pd/ γ-A1₂0₃ were examined for several oxygen partial pressure levels over the temperature range from 40–900°C using temperature-programmed reaction and slow ramp and hold temperature-time transient techniques. Combustion rates were measured by differential reaction in a fixed bed of powdered catalyst at lower temperatures (200–500°C). Also, by preparing the catalysts as thin (ca. 10 μm) coatings on an alumina tube and conducting the experiments with very high flows of dilute methane and oxygen in helium, the rate measurements were extended up to 900°C without significant contribution from gas phase reactions. The specific combustion activity of supported PdO shows a persistent hysteresis between 450 and 750°C, i.e., the rate of combustion between these temperature limits depends strongly on whether the catalyst is cooling from above 750°C or heating from below 450°C. This region is also notable for negative apparent activation energy in the rate of methane oxidation, i.e., the rate increases with decreasing temperature during reoxidation of the Pd metal and decreases with increasing temperature (especially with low oxygen partial pressure) prior to decomposition of the bulk oxide. Detailed time-temperature transient kinetic analyses were performed for supported PdO catalysts within the 450–750°C temperature range. The hysteresis in methane combustion rate is caused by a higher activation energy for reduction of oxygen chemisorbed on metallic Pd and by suppressed reoxidation of Pd metal relative to PdO decomposition.     

Catalytic combustion of methane over bimetallic Pd–Pt catalysts: The influence of support materials

The effect of support material on the catalytic performance for methane combustion has been studied for bimetallic palladium–platinum catalysts and compared with a monometallic palladium catalyst on alumina. The catalytic activities of the various catalysts were measured in a tubular reactor, in which both the activity and stability of methane conversion were monitored. In addition, all catalysts were analysed by temperature-programmed oxidation and in situ XRD operating at high temperatures in order to study the oxidation/reduction properties.

The activity of the monometallic palladium catalyst decreases under steady-state conditions, even at a temperature as low as 470 °C. In situ XRD results showed that no decomposition of bulk PdO into metallic palladium occurred at temperatures below 800 °C. Hence, the reason for the drop in activity is probably not connected to the bulk PdO decomposition.

All Pd–Pt catalysts, independently of the support, have considerably more stable methane conversion than the monometallic palladium catalyst. However, dissimilarities in activity and ability to reoxidise PdO were observed for the various support materials. Pd–Pt supported on Al₂O₃ was the most active catalyst in the low-temperature region, Pd–Pt supported on ceria-stabilised ZrO₂ was the most active between 620 and 800 °C, whereas Pd–Pt supported on LaMnAl₁₁O₁₉ was superior for temperatures above 800 °C. The ability to reoxidise metallic Pd into PdO was observed to vary between the supports. The alumina sample showed a very slow reoxidation, whereas ceria-stabilised ZrO₂ was clearly faster.     

Catalytic combustion concept for gas turbines

Catalytic combustion for gas turbines was investigated, based on a partial catalytic combustion section followed by a homogeneous combustion zone. A pressurized test rig (<25 bar) was built to test the influence of various parameters on this concept using Pd and Pt catalysts.

The pressure influence on the apparent catalytic reaction rate was of the order 0.4, assuming that the reaction kinetics could be described by a power rate function which was of first order with respect to methane. Pd catalysts showed a pressure-dependent temperature for the transition of the active PdO to the much less active Pd. Combining Pd and Pt within one catalyst resulted in a considerably lower transition temperature.

Homogeneous combustion reactions set on from 650°C, depending on the methane concentration, pressure and flow. With inlet temperatures above 800°C the homogeneous combustion always started. At outlet temperatures below 1050°C high CO concentrations could be measured. At higher temperatures the CO, CH₄ and NO_x concentrations were lower than 5 ppm. During several experiments total conversion of CH₄ and CO was observed.     

Catalytic combustion of methane over perovskites

Perovskite-type oxides of the series La_{1− x}A_xMnO₃ (A Sr, Eu and Ce) were prepared by the amorphous citrate process, leading to high surface area catalysts (up to 45 m² g⁻¹). They were tested in a flow reactor for the total combustion of methane. Complete conversion was obtained over all of the catalysts between 500 and 600°C and catalyst performance did not change significantly after 100 h on-stream. Specific activity was found to decrease monotonically with increasing the temperature of the O₂ TPD desorption peak maximum. The rate of methane combustion was low below 500°C, then grew very fast, showing that two kinds of oxygen are active in these catalysts: an adsorbed oxygen species, that reacts at low temperature, and a lattice oxygen species, that becomes available at high temperature, boosting the catalytic activity.     

Catalytic combustion over platinum group catalysts: fuel-lean versus fuel-rich operation

Performance data are presented for methane oxidation on alumina-supported Pd, Pt, and Rh catalysts under both fuel-rich and fuel-lean conditions. Catalyst activity was measured in a micro-scale isothermal reactor at temperatures between 300 and 800 °C. Non-isothermal (near adiabatic) temperature and reaction data were obtained in a full-length (non-differential) sub-scale reactor operating at high pressure (0.9 MPa) and constant inlet temperature, simulating actual reactor operation in catalytic combustion applications.

Under fuel-lean conditions, Pd catalyst was the most active, although deactivation occurred above 650 °C, with reactivation upon cooling. Rh catalyst also deactivated above 750 °C, but did not reactivate. Pt catalyst was active above 600 °C. Fuel-lean reaction products were CO₂ and H₂O for all three catalysts.

The same catalysts tested under fuel-rich conditions demonstrated much higher activity. In addition, a ‘lightoff’ temperature was found (between 450 and 600 °C), where a stepwise increase in reaction rate was observed. Following ‘lightoff’ partial oxidation products (CO, H₂) appeared in the mixture, and their concentration increased with increasing temperature. All three catalysts exhibited this behavior.

High-pressure (0.9 MPa) sub-scale reactor and combustor data are shown, demonstrating the benefits of fuel-rich operation over the catalyst for ultra-low emissions combustion.     

Low temperature diesel soots combustion using copper based catalysts modified by niobium and potassium promoters

Gravimetric temperature programmed oxidation was used to study the combustion of a diesel soot mixed with copper catalysts supported on La₂O₃ or La₂O₂CO₃. In a first step, different systems associating copper oxide with an other metal oxide were prepared and tested in presence of SO₂. The association of copper and niobium was found the most active. The influence of alkali on the activity was also studied. It results that potassium is the most effective in lowering the combustion temperature domain in agreement with literature. Finally, Cu---Nb---K catalysts deposited on lanthanum oxide have an improved catalytic activity at low temperatures compared to Cu---V---K or Cu---Mo---K/TiO₂, reported in literature. For this catalyst, the maximum oxidation rate was observed at ca. 300°C with the combustion starting at about 250°C. A similar behaviour is obtained when replacing Nb by Ta or the support La₂O₃ by either La₂O₂CO₃ or TiO₂.     

Catalytic activity of PdO/ZrO2 catalyst for methane combustion

Catalytic activity of ZrO₂ supported PdO catalysts for methane combustion has been investigated in comparison with Al₂O₃ supported PdO catalysts. It was found that the drop of catalytic activity owing to decomposition of PdO at a high temperature region (600–900°C) was suppressed by using ZrO₂ support. Temperature-programmed reduction (TPR) measurements of the catalyst with hydrogen revealed that the PdO of PdO/Al₂O₃ catalyst was reduced at the temperature less than 100°C, whereas in PdO/ZrO₂ catalyst the consumption of hydrogen was also observed at 200–300°C. This result indicates that the stable PdO species were present in the PdO/ZrO₂ catalyst. In order to confirm the formation of the solid solution of PdO and ZrO₂, X-ray diffraction (XRD) analyses of the mixtures of ZrO₂ and PdO calcined at 700–900°C in air were carried out. The lattice volume of ZrO₂ in the mixture was larger than that of ZrO₂. Furthermore, the Pd thin film on ZrO₂ substrate was prepared as a model catalyst and the depth profile of the elements in the Pd thin film was measured by Auger electron spectroscopy (AES). It was confirmed that Zr and O as well as Pd were present in the Pd thin film heated at 900°C in air. It was considered that the PdO on ZrO₂ support might be stabilized by the formation of the solid solution of PdO and ZrO₂.     

Development of a catalytically assisted combustor for a gas turbine

A catalytically assisted low NO_x combustor has been developed which has the advantage of catalyst durability. This combustor is composed of a burner section and a premixed combustion section behind the burner section. The burner system consists of six catalytic combustor segments and six premixing nozzles, which are arranged alternately and in parallel. Fuel flow rate for the catalysts and the premixing nozzles are controlled independently. The catalytic combustion temperature is maintained under 1000°C, additional premixed gas is injected from the premixing nozzles into the catalytic combustion gas, and lean premixed combustion at 1300°C is carried out in the premixed combustion section. This system was designed to avoid catalytic deactivation at high temperature and thermal or mechanical shock fracture of the honeycomb monolith. In order to maintain the catalyst temperature under 1000°C, the combustion characteristics of catalysts at high pressure were investigated using a bench scale reactor and an improved catalyst was selected for the combustor test. A combustor for a 20 MW class multi-can type gas turbine was designed and tested under high pressure conditions using LNG fuel. Measurements of NO_x, CO and unburned hydrocarbon were made and other measurements were made to evaluate combustor performance under various combustion temperatures and pressures. As a result of the tests, it was proved that NO_x emission was lower than 10 ppm converted at 16% O₂, combustion efficiency was almost 100% at 1300°C of combustor outlet temperature and 13.5 ata of combustor inlet pressure.     

Preparation and characterisation of supported La0.8Sr0.2MnO3+x

Three supported La_0.8Sr_0.2MnO_3+x catalysts were prepared, one supported on lanthanum-stabilised alumina and two supported on a NiAl₂O₄ spinel. The catalysts were characterised using X-ray diffraction, transmission electron microscopy and surface area measurements following heat-treatments at temperatures up to 1200°C in air. In the alumina-supported catalyst, a reaction occurred between the active phase and the support at high temperatures, indicating that these materials would be unsuitable for high temperature catalytic combustion. Only in the NiAl₂O₄-supported catalysts were the supported perovskite phases found to be stable at high temperature. These catalysts showed good methane combustion activity.     

Monodispersed gold nanoparticles supported on γ-Al2O3 for enhancement of low-temperature catalytic oxidation of CO

Monodispersed nano-Au/γ-Al₂O₃ catalysts for low-temperature oxidation of CO have been prepared via a modified colloidal deposition route, which involves the deposition of dodecanethiolate self-assembled monolayer (SAM)-protected gold nanoparticles (C₁₂ nano-Au) in hexane on γ-Al₂O₃ at room temperature. The diameter of the gold nanoparticles deposited on the support is 2.5 ± 0.8 nm after thermal treatment, and their valence states comprise both the metallic and oxidized states. It is found that the thermal treatment temperature affects significantly the catalytic activity of the catalysts in the processing steps. The catalyst treated at 190 °C exhibits considerably higher activity as compared to catalysts treated at 165 and 250 °C. A 2.0-wt.% nano-Au/γ-Al₂O₃ catalyst treated at 190 °C for 15 h maintains the catalytic activity at nearly 100% CO oxidation for at least 800 h at 15 °C, at least 600 h at 0 °C, and even longer than 450 h at −5 °C. Evidently, the catalysts obtained using this preparation route show high catalytic activity, particularly at low temperatures, and a good long-term stability.     

YBa2Cu3Ox as an electroconductive catalyst for combustion of carbon monoxide

YBa₂Cu₃O_x, known as a high-Tc superconductor, was used as an electroconductive catalyst and its characteristics in CO oxidation were investigated. Charging 3 V, direct current, heated YBa₂Cu₃O_x up to about 500°C, at which it could catalyze CO oxidation. Thus, this oxide has proper features required for electrically temperature-controlled combustion catalysts: one is self-heating property caused by electric current (Joule's heat) and the other is catalytic activity for combustion. The catalytic activity of YBa₂Cu₃O_x was greatly affected by the oxygen deficiency in the solid which was directly related to the partial pressure of oxygen in the reaction system.     

High-pressure reaction and emissions characteristics of catalytic reactors for gas turbine combustors

The reaction and emissions characteristics of catalytic reactors comprising noble metal catalysts were investigated using homogeneous mixtures of natural gas and vitiated air at pressures up to 2.9 MPa. The mixture temperatures at inlet ranged from 500 to 700°C and the fuel-air ratio was increased till the exit gas temperature reached about 1200°C. Values of combustion efficiency greater than 99.5% and nitrogen oxides emissions for all catalytic reactors tested were less than 0.2 g NO₂/kg fuel (2 ppm (15% 0₂) ) for all reactors at reactor exit gas temperatures higher than about 1100°C. Combustion efficiency decreased with increasing pressure in the heterogeneous-reaction controlled region, though a pressure increase favored homogeneous, gas phase reactions. Appreciable reactivity deterioration by aging for 1000 h at 1000°C was observed at lower mixture temperatures. A two-stage combustor comprising a conventional flame combustion stage and a catalytic stage was fabricated and its NO,_x emissions and performance were evaluated at conditions typical of stationary gas turbine combustor operations. About 80% reduction in NO,_x emissions levels compared with flame combustion was attained at 1 MPa pressure and 1180°C exit gas temperature, together with complete hydrocarbon combustion.     

CNG engines exhaust gas treatment via Pd-Spinel-type-oxide catalysts

Four spinel-type catalysts AB₂O₄ (CoCr₂O₄, MnCr₂O₄, MgFe₂O₄ and CoFe₂O₄) were prepared and characterized by XRD, BET, TEM and FESEM techniques. The activity of these catalysts towards the combustion of methane was evaluated in a temperature-programmed combustion (TPC) apparatus. Spinel-type-oxides containing Cr at the B site were found to provide the best results. The half-conversion temperature of methane over the CoCr₂O₄ catalyst was 376 °C with a W/F = 0.12 g s/cm⁻³. On the basis of temperature-programmed oxygen desorption (TPD) analysis as well as of catalytic combustion runs, the prevalent activity of the CoCr₂O₄ catalyst could be explained by its higher capability to deliver suprafacial, weakly chemisorbed oxygen species. This catalyst, promoted by the presence of 1 wt% of palladium deposited by wet impregnation, was lined on cordierite monoliths and then tested in a lab-scale test rig. The combination of Pd and CoCr₂O₄ catalysts enables half methane conversion at 330 °C (GHSV = 10,000 h⁻¹), a performance similar to that of conventional 4 wt% Pd-γ-Al₂O₃ catalysts but enabled with just a four-fold lower amount of noble metal.     

Low temperature incineration of mixed wastes using bulk metal oxide catalysts

Volume reduction of low-level mixed wastes from former nuclear weapons facilities is a significant environmental problem. Processing of these materials presents unique scientific and engineering problems due to the presence of minute quantities of radionuclides which must be contained and concentrated for later safe disposal. Low-temperature catalytic incineration is one option that has been utilized at the Rocky Flats facility for this purpose.

This paper presents results of research regarding evaluation of bulk metal oxides as catalysts for low-temperature incineration of carbonaceous residues which are typical by-products of fluidized bed combustion of mixed wastes under oxygen-lean conditions. A series of 14 metal oxides were screened in a thermogravimetric analyzer, using on-line mass spectrometry for speciation of reaction product gases. Catalyst evaluation criteria focused on the thermal—redox activity of the metals using both carbon black and PVC char as surrogate waste materials. Results indicated that metal oxides which were P-type semiconductor materials were suitable as catalysts for this application. Oxides of cobalt, molybdenum, vanadium, and manganese were found to be particularly stable and active catalysts under conditions specific to this process (T < 650°C, low oxygen partial pressures).

Bench-scale evaluation of these metal oxides with respect to stability to chlorine (HCl) attack was carried out at 550°C using a TG/MS system. Cobalt oxide was found to be resistant to metal loss in a HCl/He gaseous environment while metal loss from Mo, Mn, and V-based catalysts was moderate to severe. XRD and SEM/EDX analysis of spent Co catalysts indicated the formation of non-stoichiometric cobalt chlorides. Regeneration of chlorinated cobalt was found to successfully restore the low-temperature combustion activity to that of the fresh metal oxide.     

A comparative study of supported MoO3 catalysts prepared by the new “slurry” impregnation method and by the conventional method: their activity in transesterification of dimethyl oxalate and phenol

A new preparation method for supported MoO₃ catalyst, slurry impregnation, has been described and compared with the conventional impregnation method. Slurry MoO₃/water is used instead of the solution ammonium heptamolybdate, AHM [(NH₄)₆Mo₇O₂₄]. The MoO₃/γ-alumina, MoO₃/active carbon, and MoO₃/silica catalysts with different Mo loadings were prepared by slurry and by conventional method. The low solubility of MoO₃ was sufficient to transport molybdenum species from solid MoO₃ to the adsorbed phase. The equilibrium was achieved after several hours at 95 °C based on the loading amount of molybdenum. Only the process of drying was needed; calcination was not necessary and was left out. This is an important advantage for active carbon support because oxidative degradation of active carbon impregnated by molybdena starts at a relatively low temperature of about 250 °C during calcination on air. The activity was tested in the transesterification of dimethyl oxalate (DMO) and phenol at 180 °C. The dependences of catalytic activity on Mo loadings for the slurry prepared catalysts were similar to the dependences for the samples prepared by the conventional impregnation method with AHM. The activities of the slurry impregnation MoO₃/γ-Al₂O₃ catalysts were almost the same as those of catalysts prepared conventionally. Although the performances of slurry impregnation MoO₃/SiO₂ catalysts for transesterification of DMO were slightly better than those of the corresponding catalysts prepared by conventional impregnation, no waste solution and no calcining nitrogenous gases were produced. Therefore, we conclude that the new slurry impregnation method for preparation of supported molybdenum catalysts is an environmentally friendly process and a simple, clean alternative to the conventional preparation using solutions of (NH₄)₆Mo₇O₂₄. The present work will lead to a remarkable improvement in the catalyst preparation for the transesterification reaction.